CN107915791A - Carrier for olefin polymerization catalyst and preparation method and catalyst component for olefin polymerization and olefin polymerization catalysis and their application - Google Patents
Carrier for olefin polymerization catalyst and preparation method and catalyst component for olefin polymerization and olefin polymerization catalysis and their application Download PDFInfo
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- CN107915791A CN107915791A CN201610880719.8A CN201610880719A CN107915791A CN 107915791 A CN107915791 A CN 107915791A CN 201610880719 A CN201610880719 A CN 201610880719A CN 107915791 A CN107915791 A CN 107915791A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
- C08F4/022—Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
- C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/651—Pretreating with non-metals or metal-free compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
- C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
Abstract
The present invention relates to alkene catalyst field, more particularly to carrier for olefin polymerization catalyst, the preparation method of carrier for olefin polymerization catalyst, catalytic component for olefinic polymerization, the application of catalyst carrier and the catalytic component for olefinic polymerization prepared by the catalyst carrier, the method in the catalyst for olefinic polymerization is prepared, for the catalyst of olefinic polymerization, application and olefine polymerizing process of the catalyst in olefinic polyreaction.Technical solution using the present invention, the alcohol adduct that chloride magnesium halide and brominated magnesium halide are formed and oxirane compound are reacted in the preparation process of the carrier for olefin polymerization catalyst, a kind of carrier with new composition can be obtained, and obtained carrier granular form is good, is substantially not present irregular particle.And carrier prepared catalyst is applied to that activity during alpha-olefin polymerization is higher, and it polymerize the heap density of obtained polymer and isotacticity and can be also improved.
Description
Technical field
The present invention relates to alkene catalyst field, and in particular to a kind of carrier for olefin polymerization catalyst, a kind of olefinic polymerization
It is prepared by the preparation method of catalyst carrier, a kind of catalytic component for olefinic polymerization, the catalyst carrier, the method
Catalyst carrier and the catalytic component for olefinic polymerization prepare for olefinic polymerization catalyst in should
With, a kind of catalyst for olefinic polymerization, application and a kind of olefinic polymerization of the catalyst in olefinic polyreaction
Method.
Background technology
It is well known that its performance is substantially better than when the Ziegler-Natta catalyst of magnesium chloride load is used for propylene polymerization
The catalyst that other carriers are loaded.Therefore, the catalyst for olefinic polymerization is by the way that halogenated titanium is loaded in activation chlorine mostly
Change on magnesium.At present, activated magnesium chloride is usually by anhydrous MgCl2Pass through dealcoholysis again after reacting generation alcohol adduct at high temperature with alcohol
It is made.In order to obtain spherical alcohol adduct, can by spray drying, misting cooling, high pressure extrusion, high-speed stirred, mulser method and
It is prepared by the methods of high-gravity rotating bed method.Specific such as patent WO99/44009 and US4399054 is by high churning under high temperature
Quenching shapes what is prepared after changing chlorination magnesium alcoholate system.
One of the preparation method of the above-mentioned spherical alcohol adduct of magnesium chloride by cryogenic quenching what is common is that cure high temperature
Alcohol adduct melt, the consumption to the energy is larger, and preparation process is complicated, and prepared by the multiple reactors joints of palpus, and obtained
Adduct particle diameter distribution is wider.In order to solve this problem, CN102040683A proposes a kind of by magnesium halide alcohol adduct and change
Compound is reacted to prepare carrier.But all it is that magnesium halide alcohol adduct melting is scattered in method used in existing document
Afterwards, compound is directly added into the system, or is added directly into after magnesium halide alcohol adduct melting is disperseed containing compound
Reactor in.Due to the property of high-viscous liquid, experiment condition is difficult to control, and this method prepares unstable result, is easily occurred
Carrier adhesion phenomenon, the shortcomings that causing carrier molding effect bad.Therefore, it is necessary to other surface-actives are added in preparation process
Agent, such as SPAN 80, SPAN 85.The addition of these materials, not only increases cost, and to the recycling of accessory substance
Have a negative impact, also increase the cost of recycling post processing.
The content of the invention
Inventors of the present invention have surprisingly found that will be chloride in the preparation process of the carrier for olefin polymerization catalyst
The alcohol adduct that magnesium halide and brominated magnesium halide are formed reacts the pattern of formed novel carriers with oxirane compound
It is very good, and adhesion phenomenon is not susceptible to, while cost will not be increased.
First purpose of the present invention is to overcome the drawbacks described above of existing carrier for olefin polymerization catalyst, and is provided
A kind of new carrier for olefin polymerization catalyst.
Second object of the present invention is to provide a kind of preparation method of carrier for olefin polymerization catalyst.
Third object of the present invention is to provide a kind of catalytic component for olefinic polymerization.
Fourth object of the present invention is that catalyst prepared by catalyst carrier as described above, method as described above carries
The application of body and the catalytic component as described above for olefinic polymerization in the catalyst for olefinic polymerization is prepared.
The 5th purpose of the present invention is to provide a kind of catalyst for olefinic polymerization.
The 6th purpose of the present invention is to provide the catalyst as described above for olefinic polymerization in olefinic polyreaction
In application.
The 7th purpose of the present invention is to provide a kind of olefine polymerizing process.
On the one hand, the present invention provides a kind of carrier for olefin polymerization catalyst, which is as shown in formula (I)
Magnesium-containing compound,
Wherein, in formula (I), R1 is the alkyl of the straight or branched of C1-C14；R2 and R3 is identical or differs, each independent
Ground for hydrogen, C1-C5 straight or branched alkyl or C1-C5 straight or branched haloalkyl；M is 0.001-10, n 1.
Second aspect, the present invention provides a kind of preparation method of carrier for olefin polymerization catalyst, this method includes following
Step：
(1) it is ROH's by mixing magnesium halide, the general formula of the magnesium halide that magnesium halide and general formula that general formula is MgClX are MgBrY
Compound, optional inert liquid medium, are mixed and heated, obtain liquefied mixture；
(2) liquefied mixture for obtaining step (1) emulsifies, and emulsification product is contacted instead with compound shown in formula (II)
Should；
In general formula R OH, R is the alkyl of C1-C14；In compound shown in formula (II)：
Wherein, R5And R6Each stand alone as hydrogen, C1-C5 straight or branched alkyl or C1-C5 straight or branched halogen
Substituted alkyl.
The third aspect, the present invention provides a kind of catalytic component for olefinic polymerization, the catalytic component contain as
Catalyst carrier and titanium compound and internal electron donor prepared by the upper catalyst carrier or method as described above is anti-
It should obtain product.
Fourth aspect, the present invention provides catalyst prepared by catalyst carrier as described above, method as described above
The application of carrier and the catalytic component as described above for olefinic polymerization in the catalyst for olefinic polymerization is prepared.
5th aspect, the present invention provides a kind of catalyst for olefinic polymerization, which contains：
(1) it is used for the catalytic component of olefinic polymerization as described above；
(2) alkyl aluminum compound；And
(3) optional external donor compound.
6th aspect, the present invention provides the catalyst as described above for olefinic polymerization in olefinic polyreaction
Using.
7th aspect, the present invention provides a kind of olefine polymerizing process, this method includes：, will under olefin polymerization conditions
One or more alkene are contacted with the catalyst as described above for olefinic polymerization.
Technical solution using the present invention, by chloride halogenation in the preparation process of the carrier for olefin polymerization catalyst
The alcohol adduct that magnesium and brominated magnesium halide are formed is reacted with oxirane compound, can be obtained a kind of with new composition
Carrier, and obtained carrier granular form is good, is substantially not present irregular particle.And carrier prepared catalyst is applied to
Activity is higher during alpha-olefine polymerizing, and polymerize the obtained heap density of polymer and isotacticity and can also be improved.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is carrier for olefin polymerization catalyst pattern optical microscope photograph prepared by preparation example 1；
Fig. 2 is carrier for olefin polymerization catalyst pattern optical microscope photograph prepared by preparation example 2；
Fig. 3 is carrier for olefin polymerization catalyst pattern optical microscope photograph prepared by contrast preparation example 1.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
According to the first aspect of the invention, the present invention provides a kind of carrier for olefin polymerization catalyst, the catalyst to carry
Body is the magnesium-containing compound as shown in formula (I),
Wherein, in formula (I), R1For the alkyl of the straight or branched of C1-C14；The preferably alkane of the straight or branched of C1-C8
Base, for example, the alkyl of the straight or branched of C1, C2, C3, C4, C5, C6, C7, C8；It is more highly preferred to, R1Selected from ethyl, positive third
Base, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, n-hexyl, n-octyl and one kind or more in 2- ethylhexyls
Kind.
R2And R3It is identical or differ, it is each independently the alkyl of straight or branched or the straight chain of C1-C5 of hydrogen, C1-C5
Or the haloalkyl of side chain；Preferably, R2And R3It is identical or differ, it is each independently the straight or branched of hydrogen, C1-C3
The haloalkyl of the straight or branched of alkyl or C1-C3, for example, R2, R3And R4It is independently each hydrogen, the straight chain of C1, C2, C3
Side chain alkyl or C1, C2, C3 straight or branched haloalkyl；Wherein, haloalkyl be preferably chloro alkyl and/or
Bromo alkyl；Preferably, R2And R3It is identical or differ, it is each independently selected from hydrogen, methyl, ethyl, chloromethyl, chloroethyl, bromine
Methyl and bromoethyl.
Wherein, m 0.001-10, n 1.
A preferred embodiment of the invention, the average particulate diameter of the carrier for olefin polymerization catalyst can be with
For 10-100 microns, preferably 20-90 microns, particle diameter distribution is less than 1.2, is preferably 0.7-0.9.In the preferred embodiment
In, the catalyst prepared by the carrier for olefin polymerization catalyst can obtain the olefin polymer with more high-bulk-density.
In the present invention, the average particulate diameter and particle diameter distribution of the carrier for olefin polymerization catalyst can use Master Sizer
2000 laser particle analyzers (being manufactured by Malvern Instruments Ltd) measure.
According to the present invention, micro water can also be carried in the carrier for olefin polymerization catalyst, the water comes from
The minor amount of water of synthesis material and reaction medium institute band.
According to the present invention, the synthesis material of the catalyst carrier include general formula be MgClX magnesium halide and general formula be
Mixing magnesium halide, the compound that general formula is ROH and the compound as shown in formula (II) of the magnesium halide of MgBrY；
Wherein, in the magnesium halide and general formula of formula M gClX are the magnesium halide of MgBrY, X and Y independently selected from for chlorine,
Bromine, the alkyl of straight or branched of C1-C14, the aryl of C6-C14, the alkoxy of C1-C14 and the aryloxy group of C6-C14；Wherein,
The magnesium halide and general formula of formula M gClX is that the magnesium halide molar ratio of MgBrY is not particularly limited, it is preferred that general formula is
The molar ratio for the magnesium halide that the magnesium halide and general formula of MgClX is MgBrY is 0.1-1000:1, more preferably 7-15:1.
In general formula R OH, R is the alkyl of C1-C14；In compound shown in formula (II)：
Wherein, R5And R6Each stand alone as hydrogen, C1-C5 straight or branched alkyl or C1-C5 straight or branched halogen
Substituted alkyl.
According to the present invention, the content for being used to prepare the above-mentioned each component of the carrier for olefin polymerization catalyst can be larger
In the range of make choice and change, for example, on the basis of the mixing magnesium halide of 1mol, general formula is the content of the compound of ROH
Can be 4-30mol, the content of compound shown in formula (II) can be 1-10mol；Preferably, using the mixing magnesium halide of 1mol as
Benchmark, the content for the compound that general formula is ROH is 6-20mol, and the content of compound shown in formula (II) is 2-6mol.
According to the present invention, the instantiation for the magnesium halide that general formula is MgClX can be but be not limited to：Magnesium chloride, Benzene Chloride
One or more in epoxide magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium.The angle ready availability from raw material, it is excellent
Elect magnesium chloride as；General formula is that the magnesium halide of MgBrY is preferably magnesium bromide.
According to the present invention, in general formula R OH, R is preferably the alkyl of C1-C8.The alkyl of the C1-C8 for example can be first
Base, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, new penta
Base, hexyl, isohesyl, heptyl, different heptyl, octyl group or iso-octyl.The instantiation for the compound that general formula is ROH can be but not
It is limited to：In ethanol, propyl alcohol, isopropanol, n-butanol, isobutanol, amylalcohol, isoamyl alcohol, n-hexyl alcohol, n-octyl alcohol and 2-Ethylhexyl Alcohol
It is one or more.
According to the present invention, in structure compound as shown in formula (II), R5And R6It is preferred that each stand alone as hydrogen, C1-C3 it is straight
The haloalkyl of the straight or branched of the alkyl or C1-C3 of chain or side chain.The instantiation of compound can shown in the formula (II)
Think but be not limited to：Ethylene oxide, propylene oxide, epoxy butane, epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and ring
One or more in oxygen bromobutane.
According to the second aspect of the invention, the present invention provides a kind of preparation method of carrier for olefin polymerization catalyst,
This method comprises the following steps：
(1) it is ROH's by mixing magnesium halide, the general formula of the magnesium halide that magnesium halide and general formula that general formula is MgClX are MgBrY
Compound, optional inert liquid medium, are mixed and heated, obtain liquefied mixture；
(2) liquefied mixture for obtaining step (1) emulsifies, and emulsification product is contacted instead with compound shown in formula (II)
Should；
In general formula R OH, R is the alkyl of C1-C14；In compound shown in formula (II)：
Wherein, R5And R6Each stand alone as hydrogen, C1-C5 straight or branched alkyl or C1-C5 straight or branched halogen
Substituted alkyl.
Wherein, the selection of the mixing magnesium halide for the magnesium halide that the magnesium halide and general formula that general formula is MgClX are MgBrY and dosage
Species than compound shown in compound that, general formula is ROH, formula (II) has been described above, and will not be described in great detail herein.
According to the present invention, mixing magnesium halide, the general formula for the magnesium halide that the magnesium halide and general formula that general formula is MgClX are MgBrY
The dosage of compound, the structure compound as shown in formula (II) for ROH can be according to expected carrier for olefin polymerization catalyst
Composition makes appropriate choice, it is preferable that on the basis of 1mol mixing magnesium halides, the dosage for the compound that general formula is ROH is 4-
30mol, the dosage of compound shown in formula (II) are 1-10mol；It is highly preferred that on the basis of 1mol mixing magnesium halides, general formula is
The dosage of the compound of ROH is 6-20mol, and the dosage of compound shown in formula (I) is 2-6mol.
According to invention, the minor amount of water in above-mentioned each reactant can also participate in forming the anti-of carrier for olefin polymerization catalyst
Should.
According to the present invention, in step (1), for be MgClX by general formula magnesium halide and general formula be MgBrY magnesium halide
Mixing magnesium halide, the compound that general formula is ROH and the blend heated condition of optional inert liquid medium do not limit especially
It is fixed, as long as the condition of the heating enables to the melting of mixing magnesium halide and reacts with general formula for the compound of ROH.
Usually, the temperature of the heating is not less than 60 DEG C, it is preferred that the condition of the heating includes：Temperature can be 80-120 DEG C,
When time can be 0.5-5 small；Preferably, the temperature is 80-100 DEG C, when the time is 0.5-3 small.
In the present invention, described " and optional inert liquid medium " refer to the inert liquid medium there may be or
It is not present, that is to say, that can be needed in the step of the invention or inert liquid medium is not required.
In the case of inert media is included in step (1), the dosage of the inert liquid medium can be according to mixing
The dosage of magnesium halide selects.Usually, on the basis of the mixing magnesium halide of 1mol, the dosage of the inert liquid medium can be with
It is preferably 2-8L for 0.8-10L.The inert liquid medium can be it is commonly used in the art it is various not with reactant and reaction production
Chemically interactive liquid medium occurs for thing.Such as：The inert liquid medium can be silicone oil and/or inert fluid hydro carbons
Solvent.Specifically, the inert liquid medium can be kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon
One or more in oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.Inert liquid medium of the present invention is special
You Xuanwei not white oil.
According to the present invention, in step (2), it can use that well known to a person skilled in the art various methods by step (1)
Obtained liquefied mixture emulsification.For example, the liquefied mixture can be carried out low velocity shear or high speed shear, thus by its
Emulsification.The stir speed (S.S.) of the low velocity shear is usually 400-800 revs/min.The method of the high speed shear is this area skill
Well known to art personnel, as disclosed in CN1151183C high-speed mixing method (that is, by the solution containing liquid halogenated magnesium adduct with
2000-5000 revs/min of speed is stirred).Further, it is also possible to method mixes the liquid with reference to disclosed in following patent
Compound emulsifies：The solution containing liquid halogenated magnesium adduct is carried out rotation in hypergravity bed disclosed in CN1267508C to disperse
(rotating speed can be 100-3000 revs/min)；CN1463990A is disclosed to contain the molten of liquid halogenated magnesium adduct
Liquid is exported in mulser with 1500-8000 revs/min of speed；US6020279 is disclosed will to contain liquid by spray-on process
The emulsifying soln of adduct of magnesium halides.
According to the present invention, in step (2), can be by emulsification product and the catalytic condition of oxirane compound
The existing various conditions that can form carrier for olefin polymerization catalyst, for example, the catalytic condition can including temperature
Think 50-120 DEG C, the time can be 20-60 minutes；Preferably, the temperature is 60-100 DEG C, and the time is 20-50 minutes.
According to the present invention, separation of solid and liquid is carried out in the product that this method can also include obtaining haptoreaction, by solid phase
Product is washed and is dried.The separation of solid and liquid can be the existing various methods that can realize solid phase and liquid phase separation,
Such as filter, press filtration or centrifugation, under preferable case, the method for the separation of solid and liquid is filter press technique.The present invention is to press filtration
Condition is not particularly limited, and is subject to the separation for fully realizing solid phase and liquid phase as far as possible.The washing can use this
Method is washed obtained solid product known to field technology personnel, for example, can use inert hydrocarbon solvent (such as：
Pentane, hexane, heptane, petroleum ether and gasoline) obtained solid product is washed.Condition of the present invention for the drying
It is not particularly limited, such as：The temperature of the drying can be 20-70 DEG C, when the time of the drying can be 0.5-10 small.
According to the present invention, the drying can carry out under normal pressure or reduced pressure.
In addition, the catalyst carrier of the olefinic polymerization prepared present invention also offers method as described above.
The third aspect, present invention also offers a kind of catalytic component for olefinic polymerization, which contains
The catalyst carrier and titanium compound of the olefinic polymerization prepared by catalyst carrier as described above and/or method as described above
And the product that internal electron donor reacts.
Catalyst according to the invention component, the carrier for olefin polymerization catalyst, titanium compound and internal electron donor
There is no particular limitation for the condition of the reaction of compound, and under preferable case, the condition of the reaction can include：Reaction temperature is 80-
130 DEG C, when the reaction time is 0.5-10 small.
More specifically, the reaction condition includes：By (- 30 DEG C to 0 of prepared catalyst carrier and titanium compound
DEG C) under conditions of -30 DEG C to 0 DEG C 20-60min is contacted, the compound after contact is then warming up to 80-130 DEG C, and rising
Temperature process in add in electron, and react 0.5-10 it is small when, obtain the present invention catalytic component, be more highly preferred to,
The step of further including the step of being washed using titanium compound to obtained product and atent solvent washing after reaction.Its
In, the atent solvent can be atent solvent commonly used in the art, for example, toluene, hexane etc..
Catalyst according to the invention component, the internal electron donor compound can be to prepare urging for olefinic polymerization
Conventional use of various internal electron donor compounds during agent, such as can be carboxylate, alcohol ester, ether, ketone, nitrile, amine
It is preferably unitary or polyhydric aliphatic race carboxylate, unitary or polynary aromatic carboxylic acid esters, binary with the one or more in silane
One or more in alcohol ester and binary ether.
Preferably, internal electron donor of the invention is diisobutyl phthalate, n-butyl phthalate, benzene two
1,3 diamyl ester of formic acid, Ethyl formate, n-propyl formate, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, acetic acid
N-propyl, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, n propyl propionate, isopropyl propionate, butyl propionate,
One or more in methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, butyl butyrate, particularly preferably adjacent benzene
Dioctyl phthalate di-n-butyl, diisobutyl phthalate, ether, propyl ether, butyl ether, amyl ether, hexyl ether, tetrahydrofuran (THF), third
One or more in ketone, butanone, 2 pentanone, methyl iso-butyl ketone (MIBK).
Catalyst according to the invention component, described in the catalytic component of olefinic polymerization, in terms of titanium elements
The weight ratio of the titanium compound, the carrier in terms of magnesium elements and internal electron donor compound can be 1:5-15:2-15,
Preferably 1:6-13:3-12.
Catalyst according to the invention component, the titanium compound can be the mistake for preparing the catalyst for olefinic polymerization
Conventional use of various titanium compounds in journey.In general, the titanium compound is general formula Ti (ORa)4-rMrCompound, wherein, Ra
For the aliphatic group of C1-C14, M F, Cl or Br, r are the integer of 1-4；The titanium compound is preferably titanium tetrachloride, tetrabormated
Titanium, titanium tetrafluoride, three butoxy titanium chlorides, dibutoxy titanium chloride, butoxy titanium chloride, triethoxy titanium chloride, diethyl
One or more in epoxide titanium chloride and ethyoxyl titanium chloride.
Catalyst according to the invention component, its can by by catalyst carrier as described above and titanium compound and
Internal electron donor reacts acquisition according to amount ratio as above under reaction condition as above.
Fourth aspect, present invention also offers catalysis prepared by catalyst carrier as described above, method as described above
Agent carrier and the catalytic component as described above for olefinic polymerization answering in the catalyst for olefinic polymerization is prepared
With.
Wherein, the alkene is preferably propylene.
5th aspect, the present invention provides a kind of catalyst for olefinic polymerization, which contains：
(1) it is used for the catalytic component of olefinic polymerization as described above；
(2) alkyl aluminum compound；And
(3) optional external donor compound.
Detailed description has been carried out in the composition of the catalytic component for olefinic polymerization above, herein not
Repeat again.
Catalyst for olefinic polymerization has used according to the present invention for olefinic polymerization according to the present invention
Catalytic component, therefore the catalyst according to the present invention for olefinic polymerization is in the catalyst as olefinic polyreaction
When, the heap density and isotacticity of the polymer polymerizeing also are improved.
According to the present invention, the alkyl aluminum can be the conventional selection of this area, for example, the general formula of the alkyl aluminum can be with
For AlR16R16′R16", wherein, R16、R16′、R16" alkyl of C1-C8 is each independently, and wherein one or two group can
Think halogen；The instantiation of the alkyl of the C1-C8 can include but is not limited to：Methyl, ethyl, propyl group, normal-butyl, isobutyl
Base, amyl group, hexyl, n-heptyl, n-octyl, the halogen can be fluorine, chlorine, bromine, iodine.Specifically, the alkyl aluminum for example may be used
With selected from triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum, tri-n-octylaluminium, a hydrogen diethyl
Base aluminium, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminium, a chlorine di-n-hexyl
Aluminium, one aluminium ethide of dichloro, one aluminium isobutyl of dichloro, one n-butylaluminum of dichloro, one n-hexyl aluminium of dichloro, Al (n-C6H13)3、Al
(n-C8H17)3、AlEt2One or more in Cl, are preferably triethyl aluminum and/or triisobutyl aluminium.
According to the present invention, the external electron donor can be various external electron donors commonly used in the art, for example, described outer
Electron donor can be the one or more in carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol, organic phosphorus compound and organo-silicon compound；
Preferably, it containing at least one Si-OR keys and general formula is (R that the external electron donor, which is,17)a(R18)bSi(OR19)cSilication close
Thing, wherein, R17、R18And R19Alkyl for C1-C18, optionally contain hetero atom, and a and b each stand alone as the integer of 0-2, and c is
The integer of 1-3, and a, b and c and for 4.Preferably, R17、R18Alkyl, cycloalkyl for C3-C10, optionally containing miscellaneous original
Son；R19For the alkyl of C1-C10, optionally contain hetero atom.Specifically, the external electron donor can for example be selected from cyclohexyl
Methyl dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane, diisobutyl dimethoxy silicon
Alkane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, cyclohexyl front three
Oxysilane, tert-butyl trimethoxy silane, tertiary hexyl trimethoxy silane, 2- ethyl piperidine base -2- tert-butyl group dimethoxys
Silane, (the fluoro- 2- propyl group of 1,1,1- tri-) -2- ethyl piperidine base dimethoxysilanes and (1,1,1-, three fluoro- 2- propyl group)-methyl
One or more in dimethoxysilane.
Typically also, described in the catalyst of olefinic polymerization, olefinic polymerization to be used for described in terms of titanium elements
Catalytic component and the alkyl aluminum dosage in terms of aluminium element molar ratio can be 1：(1-2000), is preferably 1：(20-
500)；The molar ratio of the external electron donor and the alkyl aluminum dosage in terms of aluminium element can be 0.005-0.5:1, preferably
For 0.01-0.4:1.
According to the present invention, in the preparation process for the catalyst of olefinic polymerization, alkyl aluminum and optional outer electron
Body compound can be reacted with after being mixed for the catalytic component of olefinic polymerization respectively, or can also by alkyl aluminum and optionally
External electron donor in advance mixing after mix and react with for the catalytic component of olefinic polymerization again.
6th aspect, present invention also offers the catalyst as described above for olefinic polymerization in olefinic polyreaction
Application.
According to the present invention, it is described for olefinic polymerization when by olefinic polymerization is used for for the catalyst of olefinic polymerization
Catalytic component, alkyl aluminum and optional external electron donor can be separately added into polymer reactor, added after can also mixing poly-
Close in reactor, can also use prepolymerization method commonly understood in the industry to be added to after alkene pre-polymerization in polymer reactor.
7th aspect, the present invention provides a kind of olefine polymerizing process, this method includes：, will under olefin polymerization conditions
One or more alkene are contacted with the catalyst as described above for olefinic polymerization.
The catalytic component for theing improvement is that the ad hoc approach for employing the present invention and preparing of the present invention, and the tool of alkene
Body species, the polymerisation process of alkene and condition can be same as the prior art.
According to the present invention, above-mentioned catalyst is CH especially suitable for general formula2(wherein, R is hydrogen, C1 to=CHR-The alkyl of C6 or
C6-C12 aryl) alkene homopolymerization and copolyreaction, specifically for example, ethene, propylene, 1- butylene, 2- butylene, 2- methyl-
1- butylene, 3-methyl-1-butene, 2- methyl-2-butenes, 1- amylenes, 2- amylenes, 1- hexenes and one kind or more in styrene
Kind, it is preferably the one or more in ethene, propylene, 1- butylene, 2- butylene and styrene
According to the present invention, the polymerisation of the alkene can be carried out according to existing method, specifically, in inert gas
Protection under, in liquid monomer or atent solvent containing polymerized monomer, or in the gas phase, or pass through the combination in liquid phase
Polymerization technique carries out polymerisation.The temperature of the polymerisation can be generally 0-150 DEG C, be preferably 60-90 DEG C.It is described poly-
The pressure for closing reaction can be normal pressure or higher；Such as can be 0.01-10MPa, it is preferably 0.5-5MPa.The time of polymerization is
When 0.1-5 is small, when being preferably 0.5-3 small.The pressure of the present invention refers both to gauge pressure.In the course of the polymerization process, hydrogen can be used as polymer
Molecular weight regulator is added in reaction system to adjust the molecular weight of polymer and melt index.In addition, in the polymerization of alkene
In reaction process, the inert gas, the species of solvent and dosage are known to the skilled person, and will not be described in great detail herein.
The present invention will be described in detail by way of examples below.
In embodiment and comparative example：
1st, the average particulate diameter of carrier for olefin polymerization catalyst and particle diameter distribution use Masters Sizer2000 granularities
Instrument (being manufactured by Malvern Instruments Ltd) is measured；
2nd, the apparent form of carrier for olefin polymerization catalyst passes through the model Eclipse E200 commercially available from Nikon companies
Light microscope observed；
3rd, the heap density of polyolefine powder is measured using method as defined in GB/T 1636-2008；
4th, the test method of polymer isotacticity includes：2 grams of dry polymer samples, were placed in extractor with heptan of seething with excitement
After when alkane extracting 6 is small, by residue drying to constant weight, isotacticity is calculated by the following formula：After isotacticity (%)=extracting
Polymer quality/2 × 100；
5th, the activity of catalyst=using the obtained polymer of catalyst weight/catalyst weight.
Preparation example 1
The preparation example is used to illustrate carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reaction kettle of 0.6L, 0.07mol magnesium chlorides, 0.007mol magnesium bromides, 0.96mol ethanol are added, is being stirred
Under be warming up to 90 DEG C.When isothermal reaction 2 is small.Mixture stirring at low speed (stir speed (S.S.) is 400 revs/min) is 30 minutes scattered,
To be emulsified.And epoxychloropropane 0.48mol is added in emulsification product, press filtration after half an hour is reacted, by press filtration product
Washed 5 times with hexane, be dried in vacuo, obtain catalyst support used for olefinic polymerization Z1.
By nuclear magnetic resonance and elemental analysis, the structural formula of obtained catalyst carrier Z1 is as follows：
The average particulate diameter (D50) of the carrier for olefin polymerization catalyst Z1 is 51 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.8.Particle morphology using optical microphotograph sem observation is as shown in Figure 1.It can be seen from the figure that olefinic polymerization
The particle shape of catalyst carrier Z1 is more regular, and surface is smooth, is essentially all spherical, particle size distribution compares collection
In, and there is no that irregular particle exists.
Preparation example 2
The preparation example is used to illustrate carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reaction kettle of 0.6L, 300mL white oils, 0.07mol magnesium chlorides, 0.005mol magnesium bromides, 0.48mol second are added
Alcohol, is warming up to 100 DEG C, when isothermal reaction 1 is small under agitation.By mixture stirring at low speed (stir speed (S.S.) is 600 revs/min) point
Dissipate 30 minutes, to be emulsified.And epoxychloropropane 0.45mol is added in emulsification product, press filtration after twenty minutes is reacted, will be pressed
Filter product is washed 5 times with hexane, is finally dried product vacuum, is obtained carrier for olefin polymerization catalyst Z2.
By nuclear magnetic resonance and elemental analysis, the structural formula of obtained catalyst carrier Z2 is as follows：
The average particulate diameter (D50) of the carrier for olefin polymerization catalyst Z2 is 56 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.8.Particle morphology using optical microphotograph sem observation is as shown in Figure 2.It can be seen from the figure that olefinic polymerization
The particle shape of catalyst carrier Z2 is more regular, and surface is smooth, is essentially all spherical, particle size distribution compares collection
In, and there is no that irregular particle exists.
Preparation example 3
The preparation example is used to illustrate carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reaction kettle of 0.6L, 500mL white oils, 0.07mol magnesium chlorides, 0.009mol magnesium bromides, 1.63mol second are added
Alcohol, is warming up to 80 DEG C, when isothermal reaction 3 is small under agitation.By mixture stirring at low speed (stir speed (S.S.) is 800 revs/min) point
Dissipate 30 minutes, to be emulsified.And epoxychloropropane 0.32mol is added in emulsification product, press filtration after forty minutes is reacted, will be pressed
Filter product is washed 5 times with hexane, is finally dried product vacuum, is obtained carrier for olefin polymerization catalyst Z3.
By nuclear magnetic resonance and elemental analysis, carrier for olefin polymerization catalyst Z3 structures are consistent with formula (I) structure.
The average particulate diameter (D50) of the carrier for olefin polymerization catalyst Z2 is 50 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.9.Using optical microphotograph sem observation, the particle shape of carrier for olefin polymerization catalyst Z2 is more regular, surface
It is smooth, it is essentially all spherical, particle size distribution compares concentration, and there is no that irregular particle exists.
Contrast preparation example 1
The contrast preparation example is used to illustrate reference carrier for olefin polymerization catalyst and preparation method thereof.
Method according to embodiment 1 prepares carrier for olefin polymerization catalyst, unlike, only add the chlorination of 0.08mol
Magnesium, and magnesium bromide is added without, obtain catalyst support used for olefinic polymerization DZ1.
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization DZ1 is 100 microns, particle diameter distribution
((D90-D10)/D50) is 1.6.Particle morphology using optical microphotograph sem observation is as shown in Figure 3.It can be seen from the figure that alkene
There are substantial amounts of irregular particle in polymerized hydrocarbon catalyst carrier DZ1, and surface is more coarse.
Contrast preparation example 2
The contrast preparation example is used to illustrate reference carrier for olefin polymerization catalyst and preparation method thereof.
Method according to embodiment 1 prepares carrier for olefin polymerization catalyst, unlike, only add 0.08mol bromination
Magnesium, and magnesium chloride is added without, obtain catalyst support used for olefinic polymerization DZ2.
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization DZ2 is 110 microns, particle diameter distribution
((D90-D10)/D50) is 1.8.Exist using optical microphotograph sem observation, in catalyst support used for olefinic polymerization DZ2 substantial amounts of different
Shape particle, and surface is more coarse.
Contrast preparation example 3
The contrast preparation example is used to illustrate reference carrier for olefin polymerization catalyst and preparation method thereof.
Method according to embodiment 1 prepares carrier for olefin polymerization catalyst, unlike, by ethanol with identical weight part
Octadecyl alcolol substitutes.Obtain carrier for olefin polymerization catalyst DZ3.
The average particulate diameter (D50) of the carrier for olefin polymerization catalyst DZ3 is 95 microns, particle diameter distribution ((D90-
D10)/D50) it is 1.4.Using optical microphotograph sem observation, there are substantial amounts of irregular particle in carrier for olefin polymerization catalyst DZ3,
And surface is more coarse.
Embodiment 1
The embodiment is used for the preparation for illustrating alkene provided by the invention.
(1) preparation of olefin polymerization catalysis
In the glass reaction bottle of 300mL, the titanium tetrachloride of 100mL is added, is cooled to -20 DEG C, by 40 grams by preparing
The carrier for olefin polymerization catalyst Z1 that example 1 obtains is added thereto, and stirs 30min at -20 DEG C.Afterwards, start slow
110 DEG C are warming up to, the diisobutyl phthalate of 1.5mL is added in temperature-rise period, is filtered after maintaining 30min at 110 DEG C
Remove liquid.Then, add titanium tetrachloride to wash 2 times, finally washed 3 times with hexane, olefin polymerization catalysis C1 is obtained after dry.
(3) propylene polymerization
In the stainless steel autoclave of a 5L, purged using stream of nitrogen gas, then drawn in stream of nitrogen gas
Enter hexane solution (concentration of triethyl aluminum is 0.5mmol/mL), the methylcyclohexyl of 0.05mmol of the triethyl aluminum of 1mmol
Olefin polymerization catalysis C1,1.5L (standard obtained by step (1) of dimethoxysilane, the anhydrous hexane of 10mL and 10mg
Volume) hydrogen and 2.5L liquid propene.It is warming up to 70 DEG C, and when reaction 1 is small at such a temperature, cooling, bleeds off pressure, and discharging is dry
It is dry to obtain polypropylene powder.
The activity of catalyst is 42.1KgPP/g Cat, and the heap density of gained polypropylene powder is 0.44g/cm3, isotacticity
For 98.1%, in addition, the polypropylene powder particle shape is good, special-shaped material is substantially not present.
Embodiment 2
The embodiment is used for the preparation for illustrating alkene provided by the invention.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, it is prepared by the carrier for olefin polymerization catalyst Z1
The carrier for olefin polymerization catalyst Z2 that example 2 obtains is substituted, and obtains polypropylene powder.
Catalyst activity is 41.1KgPP/gCat, and the heap density of gained polypropylene powder is 0.44g/cm3, isotacticity
For 98.2%, in addition, the polypropylene powder particle shape is good, special-shaped material is substantially not present.
Embodiment 3
The embodiment is used for the preparation for illustrating alkene provided by the invention.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, it is prepared by the carrier for olefin polymerization catalyst Z1
The carrier for olefin polymerization catalyst Z3 that example 3 obtains is substituted, and obtains polypropylene powder.
Catalyst activity is 44.5KgPP/gCat, and the heap density of gained polypropylene powder is 0.45g/cm3, isotacticity
For 98.4%, in addition, the polypropylene powder particle shape is good, special-shaped material is substantially not present.
Comparative example 1
The comparative example is used to illustrate prepared by the reference of alkene.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, the carrier for olefin polymerization catalyst Z1 contrasts
The carrier for olefin polymerization catalyst DZ1 that preparation example 1 obtains is substituted, and obtains polypropylene powder.
Catalyst activity is 32.2KgPP/gCat, and the heap density of gained polypropylene powder is 0.38g/cm3, isotacticity
For 97.8%, in addition, being all special-shaped material in the polypropylene powder particle, mobility is bad.
Comparative example 2
The comparative example is used to illustrate prepared by the reference of alkene.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, the carrier for olefin polymerization catalyst Z1 contrasts
The carrier for olefin polymerization catalyst DZ2 that preparation example 2 obtains is substituted, and obtains polypropylene powder.
Catalyst activity is 32.4KgPP/gCat, and the heap density of gained polypropylene powder is 0.37g/cm3, isotacticity
For 97.2%, in addition, being all special-shaped material in the polypropylene powder particle, mobility is bad.
Comparative example 3
The comparative example is used to illustrate prepared by the reference of alkene.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, the carrier for olefin polymerization catalyst Z1 contrasts
The carrier for olefin polymerization catalyst DZ3 that preparation example 3 obtains is substituted, and obtains polypropylene powder.
Catalyst activity is 31.5KgPP/gCat, and the heap density of gained polypropylene powder is 0.36g/cm3, isotacticity
For 97.2%, in addition, being all special-shaped material in the polypropylene powder particle, mobility is bad.
As can be seen from the above results, the olefinic polymerization with new composition that method using the present invention is prepared is urged
The particle shape of agent carrier is good, surface is smooth, is not in irregular particle substantially, and being urged with prepared by the carrier of gained
When agent is used for alkene (particularly propylene) polymerization, the activity of catalyst is high, additionally it is possible to improve polymerizate heap density and
Isotacticity, the appearance substantially without opposite sex material.In addition, it can be seen that new composition from the contrast of embodiment 1 and comparative example 1
Carrier for olefin polymerization catalyst not only pattern is preferable, catalyst be applied to alpha-olefin polymerization constantly activity it is higher, and
Bulk density and isotacticity to olefin polymerization is also higher, great prospects for commercial application.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (20)
1. a kind of carrier for olefin polymerization catalyst, which is the magnesium-containing compound as shown in formula (I),
Wherein, in formula (I), R1For the alkyl of the straight or branched of C1-C14；R2And R3It is identical or differ, it is each independently
Hydrogen, C1-C5 straight or branched alkyl or C1-C5 straight or branched haloalkyl, wherein, m 0.001-10, n are
1。
2. catalyst carrier according to claim 1, wherein, R1For the alkyl of the straight or branched of C1-C8；Preferably, R1
Selected from ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, n-hexyl, n-octyl and 2- ethylhexyls
In one or more；
R2And R3It is identical or differ, it is each independently hydrogen, the alkyl of straight or branched of C1-C3 or the straight chain of C1-C3 or branch
The haloalkyl of chain；Preferably, R2And R3It is identical or differ, it is each independently selected from hydrogen, methyl, ethyl, chloromethyl, chloroethene
Base, bromomethyl and bromoethyl.
3. catalyst carrier according to claim 1 or 2, wherein, the average particulate diameter of the catalyst carrier is 10-
100 microns, particle diameter distribution is less than 1.2；Preferably, the average particulate diameter of the catalyst carrier is 30-70 microns, particle diameter point
Cloth is 0.7-0.9.
4. catalyst carrier according to claim 1, wherein, the synthesis material of the catalyst carrier is including general formula
Compound that mixing magnesium halide, the general formula for the magnesium halide that the magnesium halide and general formula of MgClX is MgBrY are ROH and such as formula (II) institute
The compound shown；
Wherein, in the magnesium halide and general formula of formula M gClX are the magnesium halide of MgBrY, X and Y independently selected from for chlorine, bromine,
The alkyl of the straight or branched of C1-C14, the aryl of C6-C14, the aryloxy group of the alkoxy of C1-C14 and C6-C14；
In general formula R OH, R is the alkyl of the straight or branched of C1-C14；In compound shown in formula (II)：
Wherein, R5And R6Each stand alone as hydrogen, C1-C5 straight or branched alkyl or C1-C5 straight or branched alkyl halide
Base.
5. catalyst carrier according to claim 4, wherein, on the basis of the mixing magnesium halide of 1mol, general formula is ROH's
The content of compound is 4-30mol, and the content of compound shown in formula (II) is 1-10mol；
Preferably, on the basis of 1mol mixing magnesium halides, the content for the compound that general formula is ROH is 6-20mol, shown in formula (II)
The content of compound is 2-8mol.
6. catalyst carrier according to claim 4 or 5, wherein, the magnesium halide that general formula is MgClX is selected from magnesium chloride, chlorine
Change the one or more in phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium；The magnesium halide that general formula is MgBrY is
Magnesium bromide.
7. the catalyst carrier according to claim 5 or 6, the halogenation that the magnesium halide and general formula that general formula is MgClX are MgBrY
The molar ratio of magnesium is 0.1-1000:1.
8. catalyst carrier according to claim 4 or 5, wherein, in general formula R OH, R is the straight or branched of C1-C8
Alkyl；Preferably, the compound that general formula is ROH is selected from ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, different
One or more in amylalcohol, n-hexyl alcohol, n-octyl alcohol and 2-Ethylhexyl Alcohol.
9. catalyst carrier according to claim 4 or 5, wherein, in structure compound as shown in formula (II), R5And R6
It is each independently the haloalkyl of the straight or branched of hydrogen, the alkyl of C1-C3 straight or brancheds or C1-C3；Preferably, formula
(II) compound is selected from ethylene oxide, propylene oxide, epoxy butane, epoxychloropropane, epoxy chlorobutane, epoxy bromopropane and ring
One or more in oxygen bromobutane.
10. a kind of preparation method of carrier for olefin polymerization catalyst, this method comprise the following steps：
(1) chemical combination for being ROH by mixing magnesium halide, the general formula of the magnesium halide that magnesium halide and general formula that general formula is MgClX are MgBrY
Thing, optional inert liquid medium, are mixed and heated, obtain liquefied mixture；
(2) liquefied mixture obtained step (1) emulsifies, and by compound haptoreaction shown in emulsification product and formula (II)；
In general formula R OH, R is the alkyl of C1-C14；In compound shown in formula (II)：
Wherein, R5And R6Each stand alone as hydrogen, C1-C5 straight or branched alkyl or C1-C5 straight or branched alkyl halide
Base.
11. according to the method described in claim 9, wherein, on the basis of the mixing magnesium halide of 1mol, general formula is the chemical combination of ROH
The dosage of thing is 4-30mol, and the dosage of compound shown in formula (II) is 1-10mol；
Preferably, on the basis of the mixing magnesium halide of 1mol, the dosage of the compound that general formula is ROH is 6-20mol, formula (II) institute
The dosage for showing compound is 2-8mol.
12. the method according to claim 10 or 11, wherein, in step (1), the temperature of the heating is 80-120 DEG C,
When time is 0.5-5 small；Preferably, the temperature of the heating is 80-100 DEG C, when the time is 0.5-3 small.
13. the method according to claim 10 or 11, wherein, in step (2), the catalytic condition includes temperature
For 50-120 DEG C, the time is 20-60 minutes；Preferably, it is 60-100 DEG C that the catalytic condition, which includes temperature, and the time is
20-50 minutes.
14. the method according to claim 10 or 11, wherein, on the basis of the magnesium halide of 1mol, the inert fluid is situated between
The dosage of matter is 0.8-10L；The inert liquid medium is silicone oil and/or inert fluid varsol；
Preferably, the inert liquid medium is kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, methyl
One or more in ethyl silicon oil, phenyl silicone oil and methyl phenyl silicone oil.
15. a kind of catalytic component for olefinic polymerization, which contains by any one institute in claim 1-9
Catalyst carrier prepared by the method in the catalyst carrier and/or claim 10-14 stated described in any one is closed with titanizing
The product that thing and internal electron donor react.
16. catalytic component according to claim 15, wherein, the titanium compound in terms of titanium elements, with magnesium elements
The carrier of meter and the weight ratio of internal electron donor compound are 1：5-15：2-15, is preferably 1：6-13：3-12.
17. the side in the catalyst carrier, claim 10-14 in claim 1-9 described in any one described in any one
The catalytic component for olefinic polymerization described in catalyst carrier and claim 15 or 16 prepared by method is used in preparation
Application in the catalyst of olefinic polymerization.
18. a kind of catalyst for olefinic polymerization, which contains：
(1) catalytic component for olefinic polymerization described in claim 15 or 16；
(2) alkyl aluminum compound；And
(3) optional external donor compound.
19. the application for the catalyst of olefinic polymerization in olefinic polyreaction described in claim 18.
20. a kind of olefine polymerizing process, this method include：, will by one or more alkene and right under olefin polymerization conditions
The catalyst for olefinic polymerization described in 18 is asked to contact.
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|---|---|---|---|---|
| CN111072803A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Olefin polymerization catalyst carrier, preparation method and application thereof |
| CN111072803B (en) * | 2018-10-19 | 2022-07-12 | 中国石油化工股份有限公司 | Olefin polymerization catalyst carrier, preparation method and application thereof |
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